CN106084294A - A kind of beta diketone class organotin PVC heat stabilizer and preparation method thereof - Google Patents
A kind of beta diketone class organotin PVC heat stabilizer and preparation method thereof Download PDFInfo
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- CN106084294A CN106084294A CN201610447395.9A CN201610447395A CN106084294A CN 106084294 A CN106084294 A CN 106084294A CN 201610447395 A CN201610447395 A CN 201610447395A CN 106084294 A CN106084294 A CN 106084294A
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- Prior art keywords
- heat stabilizer
- beta
- pvc heat
- preparation
- organotin pvc
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- 239000012760 heat stabilizer Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 125000005594 diketone group Chemical group 0.000 title abstract 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 46
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- 230000004044 response Effects 0.000 claims description 26
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 23
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- 239000012065 filter cake Substances 0.000 claims description 14
- 239000000376 reactant Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 6
- 239000001119 stannous chloride Substances 0.000 claims description 6
- 235000011150 stannous chloride Nutrition 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 claims description 2
- 229910000375 tin(II) sulfate Inorganic materials 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims 1
- 239000003381 stabilizer Substances 0.000 abstract description 17
- 230000008901 benefit Effects 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 235000019270 ammonium chloride Nutrition 0.000 abstract description 2
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical compound [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 abstract description 2
- 238000002604 ultrasonography Methods 0.000 abstract description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 37
- 229920000915 polyvinyl chloride Polymers 0.000 description 37
- 239000007788 liquid Substances 0.000 description 10
- 238000001556 precipitation Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000010583 slow cooling Methods 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- HRKQOINLCJTGBK-UHFFFAOYSA-N dihydroxidosulfur Chemical compound OSO HRKQOINLCJTGBK-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 231100000252 nontoxic Toxicity 0.000 description 3
- 230000003000 nontoxic effect Effects 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000002027 dodecanoic acid esters Chemical class 0.000 description 2
- LGRLWUINFJPLSH-UHFFFAOYSA-N methanide Chemical compound [CH3-] LGRLWUINFJPLSH-UHFFFAOYSA-N 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000000069 prophylactic effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- LRQGFQDEQPZDQC-UHFFFAOYSA-N 1-Phenyl-1,3-eicosanedione Chemical compound CCCCCCCCCCCCCCCCCC(=O)CC(=O)C1=CC=CC=C1 LRQGFQDEQPZDQC-UHFFFAOYSA-N 0.000 description 1
- NYMXOOKPKJUXGU-UHFFFAOYSA-N 3-oxoicosanal Chemical compound CCCCCCCCCCCCCCCCCC(=O)CC=O NYMXOOKPKJUXGU-UHFFFAOYSA-N 0.000 description 1
- 125000006414 CCl Chemical group ClC* 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- -1 butyl ester tin derivative Chemical class 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- NZZIMKJIVMHWJC-UHFFFAOYSA-N dibenzoylmethane Chemical compound C=1C=CC=CC=1C(=O)CC(=O)C1=CC=CC=C1 NZZIMKJIVMHWJC-UHFFFAOYSA-N 0.000 description 1
- WCRDXYSYPCEIAK-UHFFFAOYSA-N dibutylstannane Chemical compound CCCC[SnH2]CCCC WCRDXYSYPCEIAK-UHFFFAOYSA-N 0.000 description 1
- HGQSXVKHVMGQRG-UHFFFAOYSA-N dioctyltin Chemical compound CCCCCCCC[Sn]CCCCCCCC HGQSXVKHVMGQRG-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- JTGNPNLBCGBCMP-UHFFFAOYSA-N tetraoctylstannane Chemical compound CCCCCCCC[Sn](CCCCCCCC)(CCCCCCCC)CCCCCCCC JTGNPNLBCGBCMP-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/132—Phenols containing keto groups, e.g. benzophenones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of beta diketone class organotin PVC heat stabilizer and preparation method thereof, belong to PVC heat stabilizer technical field.Technical scheme main points are: a kind of beta diketone class organotin PVC heat stabilizer, and its structural formula is:
Description
Technical field
The invention belongs to PVC heat stabilizer technical field, be specifically related to a kind of beta-diketon class organotin PVC heat stabilizer and
Its preparation method.
Background technology
Polrvinyl chloride (being called for short PVC) is one of five big general-purpose plastics, the price cheap with it and very prominent harmony
Can and become very good material, be also the most ancient and active kind of plastic applications, its whole world yield is only second to gather
Ethylene occupies second.China is one of big producing country of polyvinyl chloride resin, and domestic PVC industry takes through the development of more than 50 years
Obtain rapid progress, the most domestic family more than 100 of Production of PVC enterprise that has, production capacity synthetic resin at home occupy first
Position.
When general PVC is generally heated to more than 130 DEG C, just start to discharge HCl, this is because in the process manufacturing PVC
In, owing to Auto-oxidation reaction, chain termination reaction and the copolyreaction of micro amount of oxygen and side reaction that some are the clearest and the most definite create
Unstable C-Cl key, and then decomposes discharges HCl, and the continuation of PVC can be decomposed and be played catalytic action by HCl, makes
PVC is finally converted to containing undersaturated conjugated double bond structures (polyenoid sequence), such consecutive reaction, has finally resulted in big point
Occurring long polyenoid sequence in subchain, when the double key number on macromolecular chain is more than 6, PVC will variable color.
Heat stabilizer accordingly, as PVC should possess prophylactic function and passivation.Wherein prophylactic function includes two sides
Face, is on the one hand to absorb the HCl that PVC thermal degradation discharges, and is on the other hand to eliminate the unstable chlorine atom of PVC, thus prevents
The generation of HCl；Passivation is the material of PVC performance of eliminating the effects of the act, and its method is that heat stabilizer enters with polyenoid sequence compound
Row additive reaction, makes long polyenoid sequence compound shorten (making conjugated double bond number reduce).At present, on market, action effect is best
Be organic tin heat stabilizer, be the most promising heat stabilizer, especially transparent PVC prepare in application the widest
General.It mainly includes the soap of stannous methide, di-n-butyl tin and dioctyltin, maleate, mercaptides, mercapto
The types such as soap.Organic tin heat stabilizer has advantages such as good heat stability, the compatibility and the transparency, but such
Heat stabilizer is all liquid, not very convenient at aspects such as transport, storages.
Beta-diketone compounds is light stabilizer and the heat stabilizer of a kind of important thermoplastic, is widely used in
In PVC plastic and ABS resin, be mainly used as polrvinyl chloride product helps heat stabilizer.As novel PVC auxiliary heat stabilizer,
Beta-diketone compounds has the advantages such as efficient, nontoxic and multi-functional.With solid or the heat stabilizer such as liquid calcium/zinc, barium/zinc also
With, the precipitation in PVC initial coloration, transparency, long-time stability and the course of processing and " zinc burning " etc. can be substantially improved, extensively
For nontoxic transparent PVC goods such as medical treatment, packagings for foodstuff.All allow to use in food packaging applications in developed countries such as America and Europes
This product.
Summary of the invention
Present invention solves the technical problem that there is provided one can comprehensively organic tin stabilizer and beta-diketon class assist steady
The advantage determining agent, makes PVC thermostable effect more preferably beta-diketon class organotin PVC heat stabilizer.
Another technical problem that the present invention solves there is provided that a kind of operation is simple, cheaper starting materials is easy to get, reacts
The preparation method of the beta-diketon class organotin PVC heat stabilizer of the solid that efficiency is higher and reproducible.
The present invention solves that above-mentioned technical problem adopts the following technical scheme that, a kind of beta-diketon class organotin PVC is thermally-stabilised
Agent, it is characterised in that structural formula is:Wherein R is phenyl or heptadecyl.
The preparation method of beta-diketon class organotin PVC heat stabilizer of the present invention, it is characterised in that concretely comprise the following steps:
In the ultrasonic response container be provided with agitating device, it is passed through nitrogen, is subsequently adding the dichloromethane dissolved with beta-diketone compounds
Alkane solution and ammonia, drip methanol solution or the stannous of tin salt under the reaction temperature of 0-50 DEG C in ultrasonic response container
The acetone soln of salt, wherein beta-diketone compounds is 1-2:1 with the molar ratio of tin salt, opens stirring during dropping
Device and ultrasonic generator, the setpoint frequency of ultrasonic generator is 20-100KHz, stops stirring, protect after dripping
Hold ultrasonic generator to work on, after being cooled to 0 DEG C, open the steam vent on ultrasonic response container, keep the nitrogen being passed through
Gas is discharged from steam vent until reactant liquor crystallize is complete, sucking filtration reactant liquor, and filter cake methanol washs repeatedly to wash away unnecessary Asia
Pink salt, filter cake obtains beta-diketon class organotin PVC heat stabilizer after at room temperature drying.
Further preferably, described tin salt is stannous chloride, stannous sulfate or nitric acid stannous.
Further preferably, described reaction temperature is 25 DEG C.
Further preferably, the setpoint frequency of described ultrasonic generator is 80KHz.
Further preferably, described beta-diketone compounds is 1.5:1 with the molar ratio of tin salt.
The present invention compared with prior art has the advantages that
1, current existing lauric acid esters and thio-alcohol organic tin stabilizer and beta-diketone compounds auxiliary are combined
The advantage of heat stabilizer, has reached to use the effect of two kinds of materials simultaneously, has used convenient；
2, beta-diketon class organotin PVC uses tin salt as raw material, it is to avoid existing lauric acid esters and thio-alcohol
Organic tin stabilizer, needs to use the organo-tin compound containing alkyl group, such as stannous methide, the tetrabutyl in process of production
The methyl ester stannum such as stannum and tetra octyl tin or butyl ester tin derivative intermediate, have toxicity big, have smelly in such intermediate production process
Taste (particularly thio-alcohol organo-tin het stabilizer), the shortcomings such as product stability is bad；The tin salt that the present invention uses not only makes
With convenient, and nontoxic, accomplish environmental protection；And this stabilizer is solid, uses, transport, store the most very convenient.
3, in the preparation method of the beta-diketon class organotin PVC heat stabilizer of the present invention, ultrasound wave is used effectively to keep away
Exempting from the miscellaneous quality affecting product in the product of ammonium chloride bag that reaction generates, use nitrogen is with whole reaction, 0 DEG C of condition
Under, solvent is the most volatile, is volatilized with solvent by nitrogen, can not only promote crystallize, and it can be avoided that oxygen affect β-
Cyclohexadione compounds is combined with stannous ion, is effectively obtained the purest product.
Detailed description of the invention
By the following examples the foregoing of the present invention is described in further details, but this should be interpreted as this
The scope inventing above-mentioned theme is only limitted to below example, and all technology realized based on foregoing of the present invention belong to this
Bright scope.
Embodiment 1
In the ultrasonic response container be provided with agitating device, it is passed through nitrogen, is subsequently adding dissolved with 1,3-diphenyl-1,
The dichloromethane solution 300mL of 3-propanedione 22.5g (0.1mol), adds after ammonia 100mL, under the reaction temperature of 25 DEG C to
Ultrasonic response container is slowly added dropwise the methanol solution 300mL dissolved with two hydrated stannous chloride 22.5g (0.1mol), dripped
Opening agitating device and ultrasonic generator in journey, the setpoint frequency of ultrasonic generator is 20KHz, after dripping, molten
Liquid is now clear state, stops stirring, keeps ultrasonic generator to work on, and slow cooling to 0 DEG C, reactant liquor is quiet
Only, open the steam vent on ultrasonic response container, keep the nitrogen being passed through to discharge from steam vent, make nitrogen with a certain amount of
Reaction dissolvent discharges ultrasonic response container, gradually has colourless or light yellow crystal precipitation, and after 5h, crystallize is complete, and sucking filtration reacts
Liquid, filter cake methanol washs repeatedly to wash away unnecessary tin salt, and filter cake obtains 1 after at room temperature drying, 3-diphenyl-1,3-
Propanedione organotin PVC heat stabilizer 27g.
Embodiment 2
In the ultrasonic response container be provided with agitating device, it is passed through nitrogen, is subsequently adding dissolved with 1,3-diphenyl-1,
The dichloromethane solution 300mL of 3-propanedione 22.5g (0.1mol), adds after ammonia 100mL, under the reaction temperature of 0 DEG C to
Ultrasonic response container is slowly added dropwise the methanol solution 300mL dissolved with two hydrated stannous chloride 12g (0.05mol), dripped
Opening agitating device and ultrasonic generator in journey, the setpoint frequency of ultrasonic generator is 100KHz, after dripping, molten
Liquid is now clear state, stops stirring, keeps ultrasonic generator to work on, and slow cooling to 0 DEG C, reactant liquor is quiet
Only, open the steam vent on ultrasonic response container, keep the nitrogen being passed through to discharge from steam vent, make nitrogen with a certain amount of
Reaction dissolvent discharges ultrasonic response container, gradually has colourless or light yellow crystal precipitation, and after 5h, crystallize is complete, and sucking filtration reacts
Liquid, filter cake methanol washs repeatedly to wash away unnecessary tin salt, and filter cake obtains 1 after at room temperature drying, 3-diphenyl-1,3-
Propanedione organotin PVC heat stabilizer 22g.
Embodiment 3
In the ultrasonic response container be provided with agitating device, it is passed through nitrogen, is subsequently adding dissolved with 1,3-diphenyl-1,
The dichloromethane solution 300mL of 3-propanedione 22.5g (0.1mol), adds after ammonia 100mL, under the reaction temperature of 50 DEG C to
Ultrasonic response container is slowly added dropwise the methanol solution 300mL dissolved with two hydrated stannous chloride 16g (0.066mol), dripped
Opening agitating device and ultrasonic generator in journey, the setpoint frequency of ultrasonic generator is 80KHz, after dripping, molten
Liquid is now clear state, stops stirring, keeps ultrasonic generator to work on, and slow cooling to 0 DEG C, reactant liquor is quiet
Only, open the steam vent on ultrasonic response container, keep the nitrogen being passed through to discharge from steam vent, make nitrogen with a certain amount of
Reaction dissolvent discharges ultrasonic response container, gradually has colourless or light yellow crystal precipitation, and after 5h, crystallize is complete, and sucking filtration reacts
Liquid, filter cake methanol washs repeatedly to wash away unnecessary tin salt, and filter cake obtains 1 after at room temperature drying, 3-diphenyl-1,3-
Propanedione organotin PVC heat stabilizer 28g.
Embodiment 4
In the ultrasonic response container be provided with agitating device, it is passed through nitrogen, is subsequently adding dissolved with 1,3-diphenyl-1,
The dichloromethane solution 300mL of 3-propanedione 22.5g (0.1mol), adds after ammonia 100mL, under the reaction temperature of 25 DEG C to
Ultrasonic response container is slowly added dropwise the methanol solution 300mL dissolved with 20 nitric hydrate stannous 40g (0.066mol), dropping
During open agitating device and ultrasonic generator, the setpoint frequency of ultrasonic generator is 80KHz, after dripping,
Solution is now clear state, stops stirring, keeps ultrasonic generator to work on, and slow cooling to 0 DEG C, reactant liquor is quiet
Only, open the steam vent on ultrasonic response container, keep the nitrogen being passed through to discharge from steam vent, make nitrogen with a certain amount of
Reaction dissolvent discharges ultrasonic response container, gradually has colourless or light yellow crystal precipitation, and after 5h, crystallize is complete, and sucking filtration reacts
Liquid, filter cake methanol washs repeatedly to wash away unnecessary tin salt, and filter cake obtains 1 after at room temperature drying, 3-diphenyl-1,3-
Propanedione organotin PVC heat stabilizer 21g.
Embodiment 5
In the ultrasonic response container be provided with agitating device, it is passed through nitrogen, is subsequently adding dissolved with 1-phenyl-3-17 alkane
Base-1, the dichloromethane solution 300mL of 3-propanedione 38.5g (0.1mol), after adding ammonia 100mL, in the reaction temperature of 25 DEG C
In ultrasonic response container, the methanol solution 300mL dissolved with two hydrated stannous chloride 16g (0.066mol) it is slowly added dropwise under degree,
Opening agitating device and ultrasonic generator during dropping, the setpoint frequency of ultrasonic generator is 80KHz, drips
After, solution is now clear state, stops stirring, keeps ultrasonic generator to work on, slow cooling to 0 DEG C, reaction
Liquid is static, opens the steam vent on ultrasonic response container, keeps the nitrogen being passed through to discharge from steam vent, makes nitrogen with certain
The reaction dissolvent of amount discharges ultrasonic response container, gradually has colourless or light yellow crystal precipitation, and after 5h, crystallize is complete, and sucking filtration is anti-
Answering liquid, filter cake methanol washs repeatedly to wash away unnecessary tin salt, and filter cake obtains 1-phenyl-3-17 alkane after at room temperature drying
Base-1,3-propanedione organotin PVC heat stabilizer 46g.
Embodiment 6
Heat stability testing
PVC material formula needed for detection consists of: the PVC material of 100 weight, the plasticizer O-phthalic of 5 weight portions
Dioctyl phthalate, the titanium dioxide of 3 weight portions and a certain amount of heat stabilizer, plasticate under the conditions of 180 DEG C in twin-screw extruder
To variable color, the length (time the longest explanation stabilizer effect is the best) of the time experienced when observing color change, above-mentioned each
The stabilizer addition that part PVC material is used is as shown in the table.
| 5% | 10% | 15% | |
| Tradition lead complex stabilizer | 10min | 18min | 21min |
| Calcium-zinc composite stabilizing agent | 12min | 20min | 24min |
| Tradition organic tin stabilizer | 15min | 24min | 32min |
| 1,3-diphenyl-1,3-propanedione organic tin stabilizer | 13min | 21min | 27min |
| 1-phenyl 3-heptadecyl-1,3-propanedione organic tin stabilizer | 16min | 22min | 30min |
As can be seen from the above table, 1 obtained by the present invention, 3-diphenylpropane-1，3-dione organic tin stabilizer and 1-benzene
Base 3-heptadecyl-1,3-propanedione organic tin stabilizer action effect has exceeded traditional lead complex stabilizer, has reached tradition
Organic tin stabilizer level.
Embodiment above describes the ultimate principle of the present invention, principal character and advantage, the technical staff of the industry should
Understanding, the present invention is not restricted to the described embodiments, and the simply explanation present invention's described in above-described embodiment and description is former
Reason, under the scope without departing from the principle of the invention, the present invention also has various changes and modifications, and these changes and improvements each fall within
In the scope of protection of the invention.
Claims (6)
1. a beta-diketon class organotin PVC heat stabilizer, it is characterised in that structural formula is:, wherein R
For phenyl or heptadecyl.
2. the preparation method of the beta-diketon class organotin PVC heat stabilizer described in a claim 1, it is characterised in that specifically walk
Suddenly it is: in the ultrasonic response container be provided with agitating device, be passed through nitrogen, be subsequently adding dissolved with beta-diketone compounds
Dichloromethane solution and ammonia, drip the methanol solution of tin salt under the reaction temperature of 0-50 DEG C in ultrasonic response container
Or the acetone soln of tin salt, wherein beta-diketone compounds is 1-2:1 with the molar ratio of tin salt, opens during dropping
Opening agitating device and ultrasonic generator, the setpoint frequency of ultrasonic generator is 20-100KHz, stops stirring after dripping
Mix, keep ultrasonic generator to work on, after being cooled to 0 DEG C, open the steam vent on ultrasonic response container, keep logical
The nitrogen entered is discharged from steam vent until reactant liquor crystallize is complete, and sucking filtration reactant liquor, the washing of filter cake methanol is repeatedly many to wash away
Remaining tin salt, filter cake obtains beta-diketon class organotin PVC heat stabilizer after at room temperature drying.
The preparation method of beta-diketon class organotin PVC heat stabilizer the most according to claim 2, it is characterised in that: described
Tin salt be stannous chloride, stannous sulfate or nitric acid stannous.
The preparation method of beta-diketon class organotin PVC heat stabilizer the most according to claim 2, it is characterised in that: described
Reaction temperature be 25 DEG C.
The preparation method of beta-diketon class organotin PVC heat stabilizer the most according to claim 2, it is characterised in that: described
The setpoint frequency of ultrasonic generator be 80KHz.
The preparation method of beta-diketon class organotin PVC heat stabilizer the most according to claim 2, it is characterised in that: described
The molar ratio of beta-diketone compounds and tin salt be 1.5:1.
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| CN107266446A (en) * | 2017-06-05 | 2017-10-20 | 毛伸 | The piperidines and the preparation method of pyridone tin complex acted on PVC stabilizer |
| CN107266443A (en) * | 2017-06-05 | 2017-10-20 | 穆开蕊 | The preparation method of piperidines with PVC stabilizer function and pyridone tin complex |
| CN107266445A (en) * | 2017-06-05 | 2017-10-20 | 穆开蕊 | The piperidines and the preparation method of the triazole tin complex of pyrido 1,2,3 acted on PVC stabilizer |
| CN107325124A (en) * | 2017-08-14 | 2017-11-07 | 毛龙飞 | A kind of preparation method of unioresistant plastic additive |
| CN107383418A (en) * | 2017-08-18 | 2017-11-24 | 侯茜茜 | A kind of unioresistant plastic additive and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107266446A (en) * | 2017-06-05 | 2017-10-20 | 毛伸 | The piperidines and the preparation method of pyridone tin complex acted on PVC stabilizer |
| CN107266443A (en) * | 2017-06-05 | 2017-10-20 | 穆开蕊 | The preparation method of piperidines with PVC stabilizer function and pyridone tin complex |
| CN107266445A (en) * | 2017-06-05 | 2017-10-20 | 穆开蕊 | The piperidines and the preparation method of the triazole tin complex of pyrido 1,2,3 acted on PVC stabilizer |
| CN107325124A (en) * | 2017-08-14 | 2017-11-07 | 毛龙飞 | A kind of preparation method of unioresistant plastic additive |
| CN107383418A (en) * | 2017-08-18 | 2017-11-24 | 侯茜茜 | A kind of unioresistant plastic additive and preparation method thereof |
| CN107383418B (en) * | 2017-08-18 | 2019-05-17 | 广东宝利兴科技有限公司 | A kind of uvioresistant plastic additive and preparation method thereof |
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